CN1262509C - Method for treating stainless steel refining slag - Google Patents
Method for treating stainless steel refining slag Download PDFInfo
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- CN1262509C CN1262509C CNB008008272A CN00800827A CN1262509C CN 1262509 C CN1262509 C CN 1262509C CN B008008272 A CNB008008272 A CN B008008272A CN 00800827 A CN00800827 A CN 00800827A CN 1262509 C CN1262509 C CN 1262509C
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- slag
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- 239000002893 slag Substances 0.000 title claims abstract description 248
- 238000000034 method Methods 0.000 title claims abstract description 71
- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 51
- 239000010935 stainless steel Substances 0.000 title claims abstract description 51
- 238000007670 refining Methods 0.000 title claims abstract description 48
- 239000000126 substance Substances 0.000 claims abstract description 58
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000001816 cooling Methods 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 32
- 230000008569 process Effects 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 239000005864 Sulphur Substances 0.000 claims description 34
- 238000002844 melting Methods 0.000 claims description 27
- 230000008018 melting Effects 0.000 claims description 25
- 229910000831 Steel Inorganic materials 0.000 claims description 22
- 239000010959 steel Substances 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 17
- 238000011282 treatment Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000010791 quenching Methods 0.000 claims description 15
- 238000007664 blowing Methods 0.000 claims description 12
- 230000000171 quenching effect Effects 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 239000010802 sludge Substances 0.000 claims description 5
- 230000004048 modification Effects 0.000 abstract description 13
- 238000012986 modification Methods 0.000 abstract description 13
- 229910052717 sulfur Inorganic materials 0.000 abstract description 7
- 239000011593 sulfur Substances 0.000 abstract description 7
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 239000011651 chromium Substances 0.000 description 69
- 229910021540 colemanite Inorganic materials 0.000 description 22
- 239000003818 cinder Substances 0.000 description 19
- 239000007789 gas Substances 0.000 description 15
- 239000003610 charcoal Substances 0.000 description 13
- 229910052810 boron oxide Inorganic materials 0.000 description 12
- -1 boron oxide compound Chemical class 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 10
- 239000005297 pyrex Substances 0.000 description 10
- 229910052804 chromium Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229910021538 borax Inorganic materials 0.000 description 6
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 238000010079 rubber tapping Methods 0.000 description 6
- 235000010339 sodium tetraborate Nutrition 0.000 description 6
- 239000004328 sodium tetraborate Substances 0.000 description 6
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- 238000007922 dissolution test Methods 0.000 description 5
- 238000011835 investigation Methods 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- 238000012797 qualification Methods 0.000 description 4
- 238000005261 decarburization Methods 0.000 description 3
- 238000006253 efflorescence Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 206010037844 rash Diseases 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000007669 thermal treatment Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 235000019739 Dicalciumphosphate Nutrition 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 238000011284 combination treatment Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- NEFBYIFKOOEVPA-UHFFFAOYSA-K dicalcium phosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])([O-])=O NEFBYIFKOOEVPA-UHFFFAOYSA-K 0.000 description 1
- 229940038472 dicalcium phosphate Drugs 0.000 description 1
- 229910000390 dicalcium phosphate Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B5/00—Treatment of metallurgical slag ; Artificial stone from molten metallurgical slag
- C04B5/06—Ingredients, other than water, added to the molten slag or to the granulating medium or before remelting; Treatment with gases or gas generating compounds, e.g. to obtain porous slag
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
- C21C5/005—Manufacture of stainless steel
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
- C21C5/52—Manufacture of steel in electric furnaces
- C21C5/54—Processes yielding slags of special composition
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/04—Removing impurities by adding a treating agent
- C21C7/068—Decarburising
- C21C7/0685—Decarburising of stainless steel
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/04—Working-up slag
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/10—Compositions or ingredients thereof characterised by the absence or the very low content of a specific material
- C04B2111/1075—Chromium-free or very low chromium-content materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Structural Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Mechanical Engineering (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Treatment Of Steel In Its Molten State (AREA)
- Carbon Steel Or Casting Steel Manufacturing (AREA)
- Furnace Details (AREA)
Abstract
The invention provides a method for treating a stainless steel refining slag which comprises treating a slag generated in a refining process for stainless steel so as for the slag to have a basicity of 1.3 to 4.0 and then mixing the slag in molten state with a substance containing a sulfur having a valency of zero or a negative value in an amount such that the slag has a sulfur content of 0.2 wt % or more. The method can be used for modifying the above slag so that Cr<6+> does not elute from the plug substantially perfectly, which results in the effective use of the slag as a material of a pavement base which is free from the danger of environmental pollution. Particularly, in the method, It is preferred for efficient modification that after the sulfur-containing substance is mixed, the cooling of the slag mixed with the sulfur-containing substance from 1200 DEG C to 400 DEG C is carried out rapidly, i.e, within a time of 48 hours.
Description
Technical field
The present invention relates to the treatment process of stainless steel refining slag, particularly provide a kind of when stoping this slag to utilize again effectively the technology of worrying objectionable impurities stripping.
Technical background
As effective utilization of iron and steel refining by product slag, consider from reducing viewpoints such as manufacturing cost and the special-purpose stacking of reduction on-site area, be the important topic of steelmaker.As the steel-making slag effectively utilize method, usually, mainly be the purposes that is used for to the recirculation at sintering workshop and is used for backfilling material that roadbed material, civil engineering work use etc.For example, about the use at the civil engineering work backfilling material, report in river iron skill (1986, vol.18, No.1, P.20-P24) the middle a kind of method that proposes is to use the modified solidified method of slag of disintegration preventive.
Yet stainless steel refining slag (following also abbreviate as " stainless steel slag ") and other copper smelter slag are very different and a little are, contain the Cr oxide compound of several per-cents in the slag as the Cr amount.Even this Cr oxide compound is no more than the landfill prescribed value of trade waste, but sometimes also as 6 valency chromium ion strippings in water.Therefore, for the stainless steel slag as roadbed material and civil engineering work backfilling material, wishing has one not because of Cr
6+Stripping from slag and in the future environment is produced the strict countermeasure of polluting.
In order to control Cr
6+The technology of stripping also proposes several at present from the stainless steel slag.For example, a kind of stainless steel slag for molten state is disclosed in the Te Kaiping 06-171993 communique, by adding with respect to the aluminium ash of 1～30 weight % that adds the back total amount and the magnesium of 0.5～15 weight % is material, the slag that contains chromic oxide is carried out the method for modification.But this method has Cr
6+The situation of stripping is because not talkative this method is perfect treatment process.In addition, produce a lot of Dicalcium Phosphate (Feed Grade)s in the method, therefore existence makes slag atomizing situation because of its crystalline modification.
In addition, the spy open in the flat 08-104553 communique disclose a kind of for stainless Decarburising and refining after, contain slag through the molten state chromic oxide that reduction is handled and be blown into rare gas element and stir in, add the material that contains divalent sulphur and make sulphur concentration in the stove reach the method for 0.20 weight %.
But, even adopt this technology, because the difference of condition still has Cr
6+The danger of stripping.Particularly in the occasion of the stainless steel slag of handling the high chromium concn as the Cr amount surpasses 2.5 weight %, can think when adopting in the past technology Cr
6+Stripping almost be difficult to prevent fully.In addition, in slag, also there is the occasion in local high chromium concn zone, can causes the problem that stably to carry out the slag modification again.
The objective of the invention is to, the slag that contains the chromic oxide that produces in the refining operation of stainless steel is carried out modification, so that Cr
6+Stripping be prevented from fact fully.In other words, the object of the present invention is to provide a kind of environmental pollution of not worrying, making becomes possible stainless steel slag treatment process as roadbed material and civil engineering work with effective utilization of backfilling material.Particularly, the object of the present invention is to provide a kind of, even in the slag
CrAmount surpasses the stainless steel slag of the high chromium concn of 2.5 weight %, also can realize Cr
6+The treatment process of the stainless steel slag of stripping from this slag not in fact fully.
Disclosure of an invention
In making stainless steel, the method for practical application has: the whole bag of tricks such as electric furnace-AOD (Argon OxygenDecarburization) method, converter-VOD (Vacuum Oxygen Decarburization) method, Cr ore smelting reduction process converter carbon rejection processes.Contrivers etc. change operational condition in various scopes, for the various stainless steel slags that produce from these operations, with regard to Cr
6+Stripping situation from slag in water has been carried out various investigation.
From the result of investigation, discoveries such as contriver in the slag of the low molten state of basicity, are sneaked into the strong S-contained substance of the such reducing power of sulphur or sulfide when improving in the slag sulphur concentration, almost can prevent Cr fully
6+Stripping.Find also that in addition particularly this effect is influential to the speed of cooling of sneaking into the melting slag behind this S-contained substance, when chilling, can obtain beyond thought achievement.In addition, said here basicity is meant in the slag SiO in the CaO content (weight %) and slag
2The ratio of content (weight %) is referred to as CaO (weight %)/SiO
2(weight %) (below, identical).
The present invention just is being based on above-mentioned discovery and is making, and it is constructed as follows.
Promptly, the invention provides a kind of treatment process of stainless steel refining slag, this method is after the slag that will produce in the stainless steel refining process is adjusted to 1.3～4.0 basicity, the S-contained substance that will contain 0 valency or negative valency sulphur is mixed in this slag of molten state, and the sulphur concentration of slag is become more than the 0.2 weight %.
Moreover, satisfactory as these the three kinds of schemes below blending means in this processing method.
(1) after this S-contained substance being added in the receiving vessel of slag, perhaps when adding this S-contained substance, the melting slag of adjusting this basicity is discharged to blending means in this receiving vessel.(2) in can the receiving vessel of mill furnace cinder, keep adjusting the molten slag of this basicity, and the blending means of in this receiving vessel, adding this S-contained substance.(3) after refining furnace tapping, S-contained substance added to the blending means the melting slag residual, that adjust this basicity in the stove at stainless steel water.
In addition, in the method for the present application, carry out this refining with electric furnace, and have following stirring of state of stainless steel water in refining furnace, the scheme that add this S-contained substance in the molten slag of adjusting this basicity on the limit is also satisfactory.
Moreover, in the above-described all method, preferably adopt the container will maintain this melting slag to shake, or at least a method such as stir by in this melting slag, blowing and stir.
In addition, in the above-mentioned all method, should use FeS as this S-contained substance.
And then, in the above-mentioned all method, in the mixed processes of this S-contained substance, should remix contain the material of boron oxide compound, at this moment, with the B in the slag
2O
3Concentration adjustment is to more than the 0.1 weight %, and is then better.
At last, in above-mentioned all method, also provide a kind of, after mixing this S-contained substance, when making this slag cooling, in 48 hours, the slag temperature is cooled to the method that 400 ℃ speed is carried out chilling from 1200 ℃.This chilling is for effectively bringing into play the gratifying especially important method of effect of the present invention.Even this chilling is with being selected from water quenching, at least a method of cooling that wind is quenched in method and the watering method of cooling is carried out to good, and this watering method of cooling is: thickness 2m is cooled off with interior discharge, the above water watering of 0.05 ton/h of slag usefulness per ton more than 1200 ℃.
The simple declaration of accompanying drawing
Fig. 1 represents the slag (basicity: S concentration and Cr 3.0～4.0) before the slag modification
6+The relation of stripping quantity.
Fig. 2 represents middle S concentration of the slag (basicity: greater than 4.0) before the slag modification and Cr
6+The relation of stripping quantity.
Fig. 3 represents basicity of slag and Cr
6+The relation of stripping.
Fig. 4 represents the thermal treatment temp and the Cr of slag
6+The relation of stripping quantity.
Fig. 5 represents that the slag temperature is cooled to 400 ℃ of required times and Cr from 1200 ℃
6+The relation of stripping quantity.
Be the preferred plan that carries out an invention
Contrivers etc. are for the various stainless steel refining slags that contain Cr0.5～8.0 weight %, with pilot survey: the Cr after sulphur concentration in the slag and basicity of slag add in the slag for the S-contained substance that will contain 0 valency or negative valency sulphur
6+The influence of stripping quantity.
Figure 1 illustrates, be 3.0～4.0 o'clock for the basicity when the stainless steel melting, adds sulphur concentration and Cr in the slag behind this S-contained substance
6+The investigation result of the relation of stripping quantity.In addition, the dissolution test method is according to carrying out as No. 46 method of Environmental Agency's order of the strictest control method.Can distinguish during sulphur concentration less than 0.20 weight %, generation Cr is arranged in the slag from Fig. 1
6+The stripping phenomenon.
In addition, the basicity when figure 2 illustrates about the stainless steel melting is 4.0～5.0 o'clock, adds sulphur concentration and Cr in the slag behind this S-contained substance
6+The investigation result of the relation of stripping quantity.As shown in the drawing, can distinguish because the cause of basicity, though add a large amount of sulphur so that in the slag after handling sulphur concentration become 1.0 weight %, still have Cr take place
6+The stripping situation.
Therefore, contriver waits again further with regard to basicity Cr
6+The influence of stripping quantity is investigated.Fig. 3 represents to reduce to regard to sulphur concentration the stainless steel slag of 0～0.1 weight %, basicity and Cr
6+The relation of stripping quantity.Found out from Fig. 3: along with the raising of basicity, Cr
6+Stripping quantity also uprises, and this tendency especially surpasses at 4.0 o'clock in basicity and becomes remarkable.Can think as its reason: when the basicity in the slag is brought up to when surpassing 4.0, this S-contained substance is difficult in slag due to the diffusion.As hereinafter described, even add the boron oxide compound of diffusion being brought into play effect in this system, the diffusion of this S-contained substance also is inadequate.
Further also to Cr
6+The generation temperature investigate.Fig. 4 represents that basicity is 2.5, sulphur concentration is 0.22 weight %, Cr
6+Stripping quantity thermal treatment temp and Cr when under atmospheric atmosphere, carrying out thermal treatment in 100 hours, slag less than the stainless steel slag of 0.05mg/l
6+The relation of stripping quantity.From Fig. 4 as seen, in 400～1200 ℃ temperature province, generate Cr easily
6+
The authors have this phenomenon in mind, to the speed of cooling and the Cr of slag
6+The relation of stripping quantity has been done investigation.The result learns, can suppress Cr by the speed of cooling of controlling between 1200～400 ℃
6+Stripping quantity.
Fig. 5 represent with basicity be 2.5, sulphur concentration is that 0.22 weight %, Cr amount is stainless steel slag needed time and the Cr when 1200 ℃ are cooled to 400 ℃ of 3.5 weight %
6+The relation of stripping quantity.From Fig. 5 as seen, by being defined in 48 hours the cooling time will be from 1200 ℃ to 400 ℃, can make Cr
6+Stripping quantity is below 0.05mg/l.
This quick cooling method is that the present application people find first.In the technology of in background technology, describing in the past, be that to contain divalent sulfur material, aluminium ash, magnesium by interpolation be the control that material etc. is formed slag, then never disclose and also be not enlightenment being set in the quick cooling method that carries out in 48 cooling time between 1200～400 ℃.
Getting the result with above-mentioned various inquiry agencies is that further discuss on the basis again, and the result obtains following prediction, when the basicity of regulation stainless steel refining slag is when sulphur concentration becomes 0.2 weight % above below 4.0, in the slag, and Cr
6+Stripping quantity can prevent fully.And at this moment, after the material of this sulfur-bearing mixed, the melting slag temperature can obtain special effect with when carrying out chilling with interior speed from 1200 ℃ to 400 ℃ in 48 hours, and this just makes us more satisfied.
But when sulphur concentration became too high in the slag, residual a part of slag had the danger that makes sulphur concentration rising in the molten steel when refining next time in stove, so the sulphur concentration in the slag should be decided to be below the 2.0 weight %.Perhaps, it is good to carry out this processing in other container.In addition, basicity of slag was low to moderate less than 1.3 hours, and the desulfurization of molten steel is insufficient, the bad danger of the composition of generation was arranged, so be necessary to make basicity of slag to reach more than 1.3.
As known to the above-mentioned discovery, in the present application, the basicity of the slag that takes place in the stainless refining procedure, that is, and CaO/SiO
2Weight ratio be set at 1.3～4.0.Its reason is to surpass 4.0 o'clock Cr
6+Stripping to suppress effect low, and the less than 1.3 bad danger of molten steel composition that happens occasionally.More gratifying basicity is 1.5～3.0, is more preferably 1.5～2.5.Such adjusting is to add CaO or SiO according to the basicity of the slag that produces in this slag
2The source gets final product.In addition, when the slag that produces just has the alkali of above-mentioned such scope by chance, unnecessary certainly by CaO or SiO
2Regulate.
Even, the Cr that from promote slag, exists
6+Reduction or prevent Cr
6+The viewpoint of oxidation see that it is resultful sneaking into the S-contained substance that contains 0 valency or negative valency sulphur, for example, the sulfur-bearing raw material be select, mixing of FeS, the mixing of blast furnace slag etc. be effective.
The mixing time of above-mentioned this S-contained substance, as midway in decarburization blowing, will cause since due to the gasificating desulfurization qualification rate of S descend and because the increase of input S makes the S concentration increase in the stainless steel, this is undesirable.Solidify or when for want of mobile, this S-contained substance of blended can not disperse in slag full and uniformly, then prevents Cr in addition, or because of slag
6+Result of extraction descends.So after the mixing time of this S-contained substance should finish from refining, carry out during the molten state before particularly solidifying to slag from the mobile high reduction refining end back of slag.
Again, at this moment, should equably this S-contained substance be sneaked in the melting slag, can enumerate: mix the material that contains boron oxide compound, be blown into oxygen and make the slag temperature rise, stir melting slag as its concrete grammar.
The material that contains boron oxide compound can make the viscosity of slag reduce, so it has the effect that this S-contained substance of blended is spread in slag.That is, by mixing boron oxide compound, even do not carry out stove shake or adopt top blast or bottom blowing to be blown into the stirring of rare gas element the time, this S-contained substance is spread in slag.
Therefore, in the present invention, this boracic oxide material is sneaked in the mixed processes of this S-contained substance.The blending means of this moment can be before the mixing of this S-contained substance, also can carry out simultaneously afterwards.If example when going out this class boracic oxide material, can list colemanite, pyrex, Sodium Tetraborate.
In addition, for boron oxide compound, prevent the dust formation of slag when cooling in addition, only put that the mixing of this boracic oxide material also is useful to the slag modification with regard to this.For anti-efflorescence effect is more effectively played a role, boron oxide compound sneak into the B that should make in the slag
2O
3Concentration becomes more than the 0.1 weight %.But, the B in the slag
2O
3When concentration is too high, easily make the loss of refractory body remarkable, so this B
2O
3It is ideal that concentration should be controlled at below about 0.5 weight %.The mixing of above-mentioned substance not only in refining vessels such as AOD, converter, VOD, and also is effective for the melting slag in the cinder ladle.
In addition, by in slag, being blown into oxygen, utilize because the Fe in the slag, FeO are oxidized to Fe
2O
3Due to exothermic reaction, make the slag temperature rise the back when mixing with this S-contained substance the viscosity that makes slag reduces because temperature rises, so this S-contained substance is easy to spread, this is just more satisfactory.
Even, in cinder ladle, mix and contain after the S-contained substance of 0 valency or negative valency sulphur the basicity (CaO/SiO that will be taken place in the time of will containing the stainless steel refining
2) be the melting slag of the chromic oxide below 4.0 more than 1.3 in this bag after, adopt oxygen blowing lance etc. with N
2, when rare gas element such as Ar is blown in the melting slag, this S-contained substance is diffusion easily just, and is therefore satisfactory.In addition, the basicity (CaO/SiO that will be taken place in the time of in the stove that can add warm sludge, will containing the stainless steel refining
2, weight ratio) be that the S-contained substance and the boracic oxide material that will contain 0 valency or negative valency sulphur are sneaked in this slag that is molten state under the slag of the chromic oxide more than 1.3, below 4.0 state of packing into, then, with oxygen blowing lance etc. with N
2, rare gas element such as Ar is blown in the melting slag, then this S-contained substance just becomes and has spread easily, this is also satisfactory.And, also can make this S-contained substance become easy diffusion if shake the stove that can add warm sludge, satisfactory.When sneaking into boron oxide compound, can obtain better effect.
Also have, the stove of the added warm sludge among said the present invention be meant every stove that can add warm sludge all can, do not have special qualification, for example, electric furnace, converter, VOD, AOD etc. are arranged.Pack into the state of the slag in these stoves can be the slag of the state of cooling, the slag of semi-melting state, any slag of molten state.The state of the said here slag that is loaded into is meant: also can be to make the state that residues in the slag in the stove after refining in converter, VOD etc.-molten steel tapping; Also can be the state of cooling, the semi-melting state of discharging to other container after the refining, the state that dissolves the slag of state.In addition, the occasion of residual slag should be substantially free of molten steel in stove in the stove of molten steel tapping back.Its reason is, the sulphur concentration of residual molten steel rises, the impurity in the time of can becoming refining next time, so this molten steel can not use.Therefore, be necessary to get rid of, because of deslagging can cause uneconomic problem with slag.
Except the mixing of above-mentioned boron oxide compound, the stirring of melting slag also is effective for the promotion of the homogenizing of slag.Can enumerate as stirring means: for behind the stainless steel Decarburising and refining, through reduction handle, melting slag after the refining furnace tapping carries out shaking of refining furnace and/or is blown into the method for gas.In addition, in the occasion of electric furnace, because can switch on, so be effective means for stirring to melting slag.
The stirring that energising effect in the electric furnace causes is under the state that molten steel is remaining in stove, by limit directly or indirectly energising in molten steel; The limit works magnetic field to carry out in molten steel.In a word, the interaction by electric current in the molten steel and external magnetic field makes it to produce in molten steel flows, and thus slag is stirred.The caused stirring of the effect of switching on thus can be before the molten steel tapping or carrying out that molten steel is tapped midway.
When being mixed into this S-contained substance in the slag, have the danger that the sulphur content in the molten steel rises inevitably.Therefore, the time that is blended into this S-contained substance in the slag and heats will do one's utmost to shorten; Perhaps this S-contained substance being blended into after the latter stage of tapping steel, molten steel residual quantity in the stove reduce goes forward side by side in the slag again, and the electricity that works stirs, and this can be suppressed to inferior limit to the sulphur that returns to molten steel, and is therefore, satisfactory.
Consider when gas is blown into because as when using the oxidizing gas of oxygen or air and so on, then FeS is oxidized and become SO
xGas is released to stove makes the qualification rate of sulphur in slag descend outward, is good to use rare gas element therefore.As rare gas element can example N arranged
2Gas or Ar gas etc., preferred this slag per ton of its flow is 0.5～2.5m
3About/min.The blowing method of gas can be: any method such as be blown into due to immersing in the slag from the gas blow pipe of bottom blowing air port or top.
The stirring of above-mentioned mixing that contains boron oxide compound and melting slag and the mix uniformly effect that produces is implemented separately respectively also can obtain, as both and usefulness, then more remarkable performance effect, thereby the slag modification can be carried out effectively.
For the present application, in this stainless steel slag of molten state, mix after this S-contained substance, the melting slag temperature was dropped to 400 ℃ speed from 1200 ℃ to carry out chilling be gratifying with interior at 48 hours, and these chilling means do not have special qualification.Such chilling means can illustratively have: quench method or be 2m with slags per ton interior discharge, more than 1200 ℃ with the above water of the 0.05 ton/h refrigerative method etc. of sprinkling water to thickness of water quenching, wind.And these methods may be used alone, can also be used in combination.
Embodiment:
Embodiment 1
Directly use 100 tons stainless steel decarburization refining furnace, slag is carried out modification.With the top after handling, tap behind the stainless steel Decarburising and refining, through reduction, the residual slag in the bottom-blown converter is object.As required, in each batch furnace charge, add CaO or SiO
2, its basicity is transferred to 1.3～1.4.Adopt the FeS that contains negative divalent sulphur as this S-contained substance, adopt as table 1-1 and show colemanite, pyrex or the Sodium Tetraborate as shown in the 1-2, they are added in the stove that basicity regulated in the residual slag as the boracic oxide material.The condition shown in the 1-2 by table 1-1 and table, also illustration the bottom blowing of rare gas element, top blast, stove the stirring of being carried out such as shake.Any occasion all will be after combination treatment deslagging in cinder ladle.The cooling conditions of slag also is shown among table 1-1 and the table 1-2 in the lump.
From the refrigerative slag, to more than 10 stoves under each condition and every stove take sample more than 10, carry out CaO, SiO
2, sulphur, B
2O
3Analysis Deng composition.Also carry out Cr according to No. 46 rules of Environmental Agency's issue
6+Dissolution test.Basicity (the CaO/SiO that has adjusted
2, weight % than) scope, sulphur concentration after handling, B
2O
3Concentration and Cr
6+The result of recall rate is shown among table 1-1 and the table 1-2 in the lump.Herein, Cr
6+Recall rate is meant in dissolution test, the Cr of each condition
6+The test number of concentration＞0.05mg/L is with respect to the ratio of whole numbers.
From table 1-1 as seen, in the example, particularly, and although the Cr concentration in the slag is the high density that surpasses 2.5 weight %, Cr
6+Stripping be still 0.In addition, in the occasion of sneaking into the boracic oxide material, can not only prevent Cr
6+Stripping and also can also not efflorescence and make curing.
Embodiment 2
Experiment is that benchmark carries out with embodiment 1, but different on the combination process of stainless steel refining slag that the basicity adjustment is over and this S-contained substance, the usefulness each points such as treatment process of electric furnace.Each condition is shown among table 2-1 and the table 2-2.
That is, adopt the cinder ladle of 50 tons of usefulness, sneak into this S-contained substance therein, sneak into again as required (example 18,20,27,29,30 and comparative example 10,13,17,18) behind the boracic oxide material as the slag receptor of deslagging; Perhaps the blended while (example 17,19,21,26,28 and comparative example 8,11,12,15,16), discharge table 2-1 and 10～50 tons of the stainless steel refining slags of showing title shown in the 2-2.
On the other hand, with the stainless steel refining slag of this title under the state of cooling or molten state 10～50 tons be encased in converter, the electric furnace etc., this slag is become after the molten state, sneak into this S-contained substance, also sneak into the boracic oxide material more as required.
In these methods, adopt FeS or blast furnace water quenching slag as this S-contained substance, adopt colemanite, pyrex or Sodium Tetraborate as the boracic oxide material.For the part of these methods, also in slag, be blown into N
2Stir one minute, rocking furnace etc.
From cooled slag, all taking more than 10 stoves under each condition and the sample of each stove more than 10 to example, comparative example, analyze CaO, SiO
2, sulphur, B
2O
3Deng chemical constitution, simultaneously carry out Cr according to No. 46 rules of Environmental Agency's issue
6+Dissolution test.With the basicity (CaO/SiO that obtains
2, weight % than) scope, sulphur concentration, B
2O
3Concentration, Cr
6+The result of recall rate and experiment condition are shown among table 2-1 and the table 2-2 in the lump.Herein, said Cr
6+Recall rate is meant: in dissolution test, and the Cr of each condition
6+The test number of concentration＞0.05mg/L is with respect to the ratio of Total Test number.
Cr from slag
6+Recall rate as seen, example is 0%, and is more than 1.5% in comparative example.In addition, in the occasion of having mixed boron oxide compound, make the slag can not efflorescence and solidify.
Industrial applicibility
As previously discussed, according to the present invention, can prevent stripping Cr from the stainless steel slag of chromium-containing oxide fully
6+Particularly, even the Cr concentration in slag surpasses the occasion of the such high Cr concentration slag of 2.5 weight %, Cr
6+Stripping also can prevent fully.Therefore, can be effectively there be environmental pollution jeopardously to be used for roadbed material or civil engineering work with backfilling material etc. in the stainless steel slag of high Cr concentration.
Table 1-1
| No. | Basicity (the CaO/SiO of slag 2) | Cr concentration (wt%) in the slag before the modification | S-contained substance | The material that contains boron oxide compound | Top blast tolerance (Nm 3/ min t-slag) | Bottom blowing tolerance (Nm 3/ min t-slag) | |||
| Kind | Combined amount (kg/t slag) | Kind | Combined amount (kg/t slag) | ||||||
| Example | 1 | 1.3～4.0 | 2.5～6.1 | - | - | - | - | 0 | 0 |
| 2 | 1.3～4.0 | 2.5～8.2 | FeS | 10 | - | - | 0 | 0 | |
| 3 | 1.3～4.0 | 2.5～5.8 | FeS | 5 | Colemanite | 5 | 0 | 0 | |
| 4 | 1.3～4.0 | 2.5～7.5 | FeS | 5 | Colemanite | 3 | 0 | 0 | |
| 5 | 1.3～4.0 | 2.5～7.4 | FeS | 5 | Pyrex | 17 | 0 | 0 | |
| 6 | 1.3～4.0 | 2.5～5.5 | FeS | 5 | - | - | 1 | 0 | |
| 7 | 1.3～4.0 | 2.5～7.2 | FeS | 5 | - | - | 0.5 | 0 | |
| 8 | 1.3～4.0 | 2.5～6.7 | FeS | 5 | - | - | 0 | 1 | |
| 9 | 1.3～4.0 | 2.5～6.2 | FeS | 5 | - | - | 0 | 0 | |
| 10 | 1.3～4.0 | 2.5～8.0 | FeS | 5 | Colemanite | 5 | 0 | 0 | |
| 11 | 1.3～4.0 | 2.5～6.5 | FeS | 5 | Pyrex | 12 | 0 | 1 | |
| 12 | 1.3～4.0 | 2.5～7.2 | FeS | 5 | Borsyl | 4 | 0 | 0 | |
| Comparative example | 1 | 1.3～4.0 | 0.4～6.8 | FeS | 2 | - | - | 1 | 0 |
| 2 | 1.3～4.0 | 0.5～7.1 | FeS | 2 | Colemanite | 5 | 0 | 0 | |
| 3 | 4.1～5.5 | 0.4～5.5 | FeS | 20 | - | - | 0 | 0 | |
| 4 | 4.1～5.5 | 0.4～7.7 | FeS | 10 | Colemanite | 5 | 0 | 0 | |
| 5 | 4.1～5.5 | 0.4～7.7 | FeS | 10 | Colemanite | 10 | 0 | 0 | |
| 6 | 4.1～5.5 | 0.6～7.3 | FeS | 10 | Pyrex | 17 | 1 | 1 | |
| 7 | 1.3～4.0 | 0.5～7.1 | FeS | 5 | Colemanite | 5 | 0 | 0 | |
* use height to contain the S coke
* adopts the cooling of water quenching
* * adopts the quench cooling of method of wind
Table 1-2
| No. | Stove shake number of times | 1200～400 ℃ cooling time (h) | The watering cooling conditions | S concentration (wt%) in the slag | B in the slag 2O 3Concentration (wt%) | Cr 6+Recall rate (%) | ||
| The thickness of slag (m) | Watering amount (t/h-t slag) | |||||||
| Example | 1 | 0 | 24 | 1.5 | 0.08 | 0.21～0.29 * | - | 0.0 |
| 2 | 0 | 48 | 2 | 0.05 | 0.39～0.65 | - | 0.0 | |
| 3 | 0 | 48 | 1 | 0.05 | 0.21～0.40 | 0.19～0.38 | 0.0 | |
| 4 | 0 | 12 | 0.5 | 0.2 | 0.21～0.39 | 0.10～0.25 | 0.0 | |
| 5 | 0 | 48 | 2 | 0.2 | 0.22～0.41 | 0.17～0.37 | 0.0 | |
| 6 | 0 | 0.01 ** | - | - | 0.21～0.40 | - | 0.0 | |
| 7 | 0 | 24 | 1.5 | 0.08 | 0.21～0.37 | - | 0.0 | |
| 8 | 0 | 24 | 2 | 0.1 | 0.22～0.40 | - | 0.0 | |
| 9 | 3 | 48 | 2 | 0.05 | 0.21～0.39 | - | 0.0 | |
| 10 | 2 | 0.02 *** | - | - | 0.21～0.43 | 0.15～0.40 | 0.0 | |
| 11 | 0 | 48 | 1 | 0.1 | 0.23～0.35 | 0.12～0.25 | 0.0 | |
| 12 | 0 | 48 | 2 | 0.05 | 0.21～0.44 | 0.18～0.29 | 0.0 | |
| Comparative example | 1 | 0 | 0.01 ** | - | - | 0.12～0.19 | - | 4.5 |
| 2 | 3 | 4 | 0.5 | 0.2 | 0.12～0.19 | 0.20～0.37 | 2.3 | |
| 3 | 0 | 24 | 2 | 0.1 | 0.65～0.89 | - | 5.7 | |
| 4 | 0 | 24 | 1 | 0.05 | 0.37～0.55 | 0.18～0.40 | 3.0 | |
| 5 | 3 | 0.02 *** | - | - | 0.38～0.57 | 0.35～0.75 | 6.1 | |
| 6 | 0 | 24 | 2 | 0.15 | 0.34～0.53 | 0.15～0.36 | 4.7 | |
| 7 | 3 | 72 | 4 | 0.1 | 0.22～0.38 | 0.20～0.37 | 1.1 | |
* use height to contain the S coke
* adopts the cooling of water quenching
* * adopts the quench cooling of method of wind
Table 2～1 example
| No. | The slag title | Basicity (the CaO/SiO of slag 2 | Cr concentration (wt%) in the slag before the modification | S-contained substance | The boracic oxide material | Add the container of S-contained substance | N 2Amount (Nm '/min t-slag) is gone in air-blowing | Stove shake number of times | 1200～400 ℃ cooling time (h) | The watering cooling conditions | S concentration (wt%) in the slag | B in the slag 2O 3Concentration (wt%) | Cr 6+Recall rate (%) | |||
| Kind | Combined amount (kg/t slag) | Kind | Combined amount (kg/t slag) | The thickness of slag (m) | Watering amount (t/h-t slag) | |||||||||||
| 13 | Take off the charcoal slag | 1.3～ 1.8 | 1.0～3.5 | FeS | 10 | - | - | Cinder ladle | - | - | 24 | 1 | 0.05 | 0.30～ 0.62 | - | 0.0 |
| 14 | The VOD slag | 1.3～ 2.0 | 2.1～5.3 | FeS | 5 | - | - | Cinder ladle | - | - | 48 | 2 | 0.05 | 0.22～ 0.40 | - | 0.0 |
| 15 | Electric furnace slag | 3.0～ 4.0 | 4.0～8.0 | FeS | 5 | - | - | Cinder ladle | - | - | 0.01 ** | - | - | 0.21～ 0.39 | - | 0.0 |
| 16 | The AOD slag | 1.6～ 2.1 | 1.9～4.1 | FeS | 5 | - | - | Cinder ladle | 0.3 | - | 24 | 1.5 | 0.2 | 0.22～ 0.39 | - | 0.0 |
| 17 | Take off the charcoal slag | 2.2～ 3.5 | 0.6～2.9 | FeS | 5 | Colemanite | 5 | Cinder ladle | - | - | 12 | 0.5 | 0.05 | 0.22～ 0.38 | 0.20～ 0.40 | 0.0 |
| 18 | Take off the charcoal slag | 1.5～ 2.2 | 1.8～4.0 | FeS | 5 | Pyrex | 17 | Cinder ladle | - | - | 0.02 *** | - | - | 0.25～ 0.43 | 0.15～ 0.38 | 0.0 |
| 19 | The AOD slag | 1.9～ 2.6 | 3.3～4.6 | FeS | 5 | Sodium Tetraborate | 5 | Cinder ladle | - | - | 24 | 2 | 0.1 | 0.24～ 0.39 | 0.18～ 0.45 | 0.0 |
| 20 | Electric furnace slag | 2.8～ 3.5 | 2.5～5.0 | FeS | 5 | Colemanite | 5 | Cinder ladle | 0.5 | - | 48 | 2 | 0.05 | 0.22～ 0.41 | 0.15～ 0.40 | 0.0 |
| 21 | Take off the charcoal slag | 1.3～ 2.0 | 2.2～4.2 | Blast furnace water quenching slag | 150 | Colemanite | 10 | Cinder ladle | - | - | 48 | 2 | 0.05 | 0.22～ 0.41 | 0.40～ 0.62 | 0.0 |
| 22 | Take off the charcoal slag | 1.3～ 1.8 | 1.0～3.5 | FeS | 10 | - | - | Converter | - | 1 | 12 | 1 | 0.1 | 0.32～ 0.60 | - | 0.0 |
| 23 | The VOD slag | 1.3～ 2.0 | 2.1～5.3 | FeS | 5 | - | - | Converter | 0.5 | 1 | 0.01 ** | - | - | 0.25～ 0.41 | - | 0.0 |
| 24 | Electric furnace slag | 3.5～ 4.0 | 4.0～8.0 | FeS | 5 | - | - | Electric furnace | - | - | 48 | 2 | 0.05 | 0.20～ 0.39 | - | 0.0 |
| 25 | The AOD slag | 1.6～ 2.1 | 1.9～4.1 | FeS | 5 | - | - | AOD | - | - | 0.02 *** | - | - | 0.22～ 0.43 | - | 0.0 |
| 26 | Take off the charcoal slag | 2.2～ 3.5 | 0.6～2.9 | FeS | 5 | Colemanite | 5 | Converter | - | - | 24 | 1 | 0.1 | 0.20～ 0.42 | 0.15～ 0.38 | 0.0 |
| 27 | Take off the charcoal slag | 1.5～ 2.2 | 1.8～4.0 | FeS | 5 | Pyrex | 17 | Electric furnace | - | 2 | 12 | 1 | 0.2 | 0.23～ 0.46 | 0.19～ 0.39 | 0.0 |
| 28 | The AOD slag | 1.9～ 2.6 | 3.3～4.6 | FeS | 5 | Colemanite | 5 | Electric furnace | 0.3 | - | 48 | 1.5 | 0.05 | 0.28～ 0.41 | 0.16～ 0.47 | 0.0 |
| 29 | Electric furnace slag | 2.8～ 3.5 | 2.5～5.0 | FeS | 5 | Sodium Tetraborate | 5 | Converter | - | - | 48 | 2 | 0.05 | 0.20～ 0.45 | 0.16～ 0.40 | 0.0 |
| 30 | Take off the charcoal slag | 1.3～ 2.0 | 2.2～4.2 | Blast furnace water quenching slag | 150 | Colemanite | 10 | VOD | - | - | 24 | 2 | 0.07 | 0.22～ 0.41 | 0.37～ 0.55 | 0.0 |
*Adopt the cooling of shrend
* *The cooling of adopting wind to quench
Table 2-2 comparative example
| No. | The slag title | Basicity (the CaO/SiO of slag 2) | Cr concentration (wt%) in the slag before the modification | S-contained substance | The boracic oxide material | Add the container of S-contained substance | N 2Amount (Nm is gone in air-blowing 3/ min t-slag) | Stove shake number of times | 1200～400 ℃ cooling time (h) | The watering cooling conditions | S concentration (wt%) in the slag | B in the slag 2O 3Concentration (wt%) | Cr 6+Recall rate (%) | |||
| Kind | Combined amount (kg/t slag) | Kind | Combined amount (kg/t slag) | The thickness of slag (m) | Watering amount (t/h-t slag) | |||||||||||
| 8 | Take off the charcoal slag | 4.1～4.9 | 0.7～2.5 | FeS | 5 | Colemanite | 5 | Cinder ladle | - | - | 24 | 1.5 | 0.1 | 0.29～ 0.47 | 0.17～ 0.38 | 4.5 |
| 9 | Take off the charcoal slag | 1.5～2.2 | 1.5～3.5 | FeS | 2 | - | - | Cinder ladle | - | - | 12 | 1 | 0.15 | 0.10～ 0.19 | - | 2.9 |
| 10 | Electric furnace slag | 4.3～5.1 | 1.4～4.4 | FeS | 10 | Colemanite | 5 | Cinder ladle | 0.5 | - | 48 | 2 | 0.05 | 0.37～ 0.55 | 0.16～ 0.40 | 3.0 |
| 11 | The AOD slag | 1.5～2.2 | 3.0～5.8 | FeS | 2 | Colemanite | 10 | Cinder ladle | - | - | 24 | 1 | 0.05 | 0.08～ 0.15 | 0.33～ 0.7 | 4.5 |
| 12 | The VOD slag | 4.2～5.0 | 2.0～4.8 | FeS | 10 | Pyrex | 17 | Cinder ladle | - | - | 12 | 1 | 0.1 | 0.34～ 0.53 | 0.14～ 0.36 | 1.8 |
| 13 | Take off the charcoal slag | 4.1～4.9 | 0.7～2.5 | FeS | 5 | Colemanite | 5 | Converter | 0.5 | 3 | 0.01 ** | - | - | 0.31～ 0.43 | 0.15～ 0.41 | 3.2 |
| 14 | Take off the charcoal slag | 1.5～2.2 | 1.5～3.5 | FeS | 2 | - | - | Electric furnace | - | - | 0.02 *** | - | - | 0.13～ 0.19 | - | 3.0 |
| 15 | Electric furnace slag | 4.3～5.1 | 1.4～4.4 | FeS | 10 | Colemanite | 5 | Electric furnace | - | - | 48 | 2 | 0.05 | 0.36～ 0.50 | 0.18～ 0.38 | 3.5 |
| 16 | The AOD slag | 1.5～2.2 | 3.0～5.8 | FeS | 2 | Sodium Tetraborate | 10 | Converter | - | - | 24 | 1 | 0.1 | 0.10～ 0.16 | 0.35～ 0.67 | 3.8 |
| 17 | The VOD slag | 4.2～5.0 | 2.0～4.8 | FeS | 10 | Pyrex | 17 | VOD | - | - | 12 | 0.5 | 0.05 | 0.34～ 0.56 | 0.15～ 0.33 | 1.5 |
| 18 | Take off the charcoal slag | 1.5～2.2 | 1.8～4.0 | FeS | 5 | Colemanite | 5 | Electric furnace | - | 2 | 72 | 2 | 0.01 | 0.23～ 0.44 | 0.18～ 0.37 | 0.5 |
*The water quenching but
* *With the wind quenching but
Claims (10)
1. the treatment process of stainless steel refining slag, it is characterized in that, with the slag that produces in the stainless steel refining process, after adjusting to 1.3～4.0 basicity, the S-contained substance that will contain 0 valency or negative valency sulphur again mixes the sulphur concentration that makes slag and reaches more than the 0.2 weight % with this slag of molten state, when making this slag cooling, carry out chilling from 1200 ℃ of speed that drop to 400 ℃ in 48 hours, to make the slag temperature.
2. press the treatment process of the described stainless steel refining slag of claim 1, it is characterized in that, this mixing is after adding this S-contained substance the receptor of slag to, when perhaps adding this sulfocompound, the melting slag deslagging of adjusting this basicity is carried out in this receptor.
3. by the treatment process of the described stainless steel refining slag of claim 1, it is characterized in that this mixing is that the melting slag that will adjust this basicity remains in the receptor that can add warm sludge, this S-contained substance is added to carry out in this receptor again.
4. by the treatment process of the described stainless steel refining slag of claim 1, it is characterized in that this mixing is after stainless molten steel tap from refining furnace, this S-contained substance of interpolation carries out in the interior residual melting slag of adjusting this basicity of stove.
5. by the treatment process of the described stainless steel refining of claim 1 slag, it is characterized in that, carry out this refining, and in refining furnace, exist under the state of stainless molten steel and stir on one side with electric furnace, on one side this S-contained substance is added in the melting slag of adjusting this basicity.
6. by the treatment process of each described stainless steel refining slag in the claim 1～5, it is characterized in that, select for use the container that will maintain this melting slag to shake, or stir by at least a method in this melting slag, blowing.
7. by the treatment process of each described stainless steel refining slag in the claim 1～5, it is characterized in that this S-contained substance is FeS.
8. by the treatment process of each described stainless steel refining slag in the claim 1～5, it is characterized in that, in the mixed processes of this S-contained substance, also mix the boracic oxide material.
9. by the treatment process of the described stainless steel refining slag of claim 8, it is characterized in that, mix above-mentioned boracic oxide material, make the B in the slag
20
3Concentration is adjusted to 0.1 weight %～0.5 weight %.
10. press the treatment process of each described stainless steel refining slag in the claim 1～5, it is characterized in that, to be selected from quench method and thickness 2m carried out this chilling with at least a method of cooling in the above water watering method of cooling of 0.05 ton/h of slags interior discharge, more than 1200 ℃ usefulness per ton of water quenching, wind.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6275299 | 1999-03-10 | ||
| JP62752/1999 | 1999-03-10 | ||
| JP62752/99 | 1999-03-10 | ||
| JP28821/00 | 2000-02-07 | ||
| JP2000028821A JP2000319047A (en) | 1999-03-10 | 2000-02-07 | Reforming treatment of stainless steel refining slag |
| JP28821/2000 | 2000-02-07 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1304387A CN1304387A (en) | 2001-07-18 |
| CN1262509C true CN1262509C (en) | 2006-07-05 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB008008272A Expired - Fee Related CN1262509C (en) | 1999-03-10 | 2000-03-02 | Method for treating stainless steel refining slag |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US6732547B1 (en) |
| EP (1) | EP1094043A1 (en) |
| JP (1) | JP2000319047A (en) |
| KR (1) | KR100530197B1 (en) |
| CN (1) | CN1262509C (en) |
| BR (1) | BR0005311A (en) |
| CA (1) | CA2331182A1 (en) |
| TW (1) | TW500711B (en) |
| WO (1) | WO2000053539A1 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100805057B1 (en) * | 2001-12-21 | 2008-02-20 | 주식회사 포스코 | Preparation method of water granualted slag |
| KR100460096B1 (en) * | 2002-04-01 | 2004-12-04 | 주식회사 한테크 | Waste treatment method and solidified material obtained by the same method |
| KR100889685B1 (en) * | 2002-12-24 | 2009-03-19 | 주식회사 포스코 | A method for refining with high purity of stainless steel |
| JP4829225B2 (en) * | 2004-05-18 | 2011-12-07 | ホルシム テクノロジー リミティド | Chromium reduction method for metallurgical slag |
| JP5407337B2 (en) * | 2009-01-06 | 2014-02-05 | 大同特殊鋼株式会社 | Treatment method of reduced slag |
| CN102534066B (en) * | 2011-12-13 | 2013-06-26 | 河南科技大学 | High-temperature molten steel slag treating method |
| KR101131671B1 (en) | 2012-01-02 | 2012-03-28 | 황효규 | Method for treatment of industrial wastes |
| CN105039617B (en) * | 2015-09-08 | 2017-09-01 | 华北理工大学 | Store up the processing method of EAF stainless steel slags |
| CN106282746B (en) * | 2016-08-19 | 2018-05-22 | 东北大学 | A kind of method of slag bath reduction treatment electric furnace stainless steel slag |
| CN113416814B (en) * | 2021-08-25 | 2021-11-09 | 天津市新天钢钢铁集团有限公司 | Method for realizing zero emission of refining slag of LF (ladle furnace) |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1051627A (en) * | 1903-01-06 | 1913-01-28 | Atlas Portland Cement Company | Apparatus for producing cement. |
| US964805A (en) * | 1907-07-01 | 1910-07-19 | Atlas Portland Cement Company | Apparatus for producing cement. |
| US980606A (en) * | 1910-03-16 | 1911-01-03 | Heinrich Colloseus | Process of granulating molten slag. |
| US3054139A (en) * | 1956-08-22 | 1962-09-18 | George A Bartholomew | Method and apparatus for pelleting molten slag |
| US3523775A (en) * | 1967-07-10 | 1970-08-11 | United States Steel Corp | Method and apparatus for treating slag |
| US3594142A (en) * | 1968-06-05 | 1971-07-20 | Nat Slag Ltd | Processes for the pelletization of metallurgical slag |
| JP2872586B2 (en) * | 1994-10-05 | 1999-03-17 | 川崎製鉄株式会社 | Reforming method of stainless steel slag |
| JP3586311B2 (en) * | 1995-05-01 | 2004-11-10 | 新日本製鐵株式会社 | Chrome-containing steel slag and its waste treatment method |
| US6547959B1 (en) * | 2000-09-19 | 2003-04-15 | United Laboratories International, Llc | Method for treating hazardous and corrosion-inducing sulfur compounds |
-
2000
- 2000-02-07 JP JP2000028821A patent/JP2000319047A/en active Pending
- 2000-03-02 KR KR10-2000-7012506A patent/KR100530197B1/en not_active IP Right Cessation
- 2000-03-02 US US09/700,020 patent/US6732547B1/en not_active Expired - Fee Related
- 2000-03-02 CN CNB008008272A patent/CN1262509C/en not_active Expired - Fee Related
- 2000-03-02 BR BR0005311A patent/BR0005311A/en not_active Application Discontinuation
- 2000-03-02 CA CA 2331182 patent/CA2331182A1/en not_active Abandoned
- 2000-03-02 EP EP20000906634 patent/EP1094043A1/en not_active Withdrawn
- 2000-03-02 WO PCT/JP2000/001235 patent/WO2000053539A1/en not_active Application Discontinuation
- 2000-03-06 TW TW89103983A patent/TW500711B/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| KR20010043459A (en) | 2001-05-25 |
| BR0005311A (en) | 2001-01-30 |
| CA2331182A1 (en) | 2000-09-14 |
| TW500711B (en) | 2002-09-01 |
| CN1304387A (en) | 2001-07-18 |
| KR100530197B1 (en) | 2005-11-22 |
| WO2000053539A1 (en) | 2000-09-14 |
| EP1094043A1 (en) | 2001-04-25 |
| JP2000319047A (en) | 2000-11-21 |
| US6732547B1 (en) | 2004-05-11 |
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